Water based erasable ink compositions

ABSTRACT

A water base erasable ink composition which comprises: 
     (a) water as a solvent in amounts of 50-90% by weight; 
     (b) a coloring agent dispersed or dissolved in water in amounts of 1-30% by weight; 
     (c) an aqueous emulsion of at least one nonvolatile or only slightly volatile compound which is liquid at room temperatures and is selected from the group consisting of aliphatic carboxylic acid esters, higher hydrocarbons and higher alcohols in dry amounts of 1-20% by weight; and 
     (d) a water soluble resin or a water-solubilized resin which is film forming at room temperatures in amounts of 0.1-15% by weight. The water soluble resin or water-solubilized resin may be displaced by an aqueous emulsion or a hydrosol of water insoluble resins.

This application is a continuation of Ser. No. 08/124,581 filed Sep. 22,1993, now abandoned, which is a continuation of Ser. No. 08/032,157filed Mar. 12, 1993, now U.S. Pat. No. 5,561,175, which is acontinuation of Ser. No. 07/653,262 filed Feb. 11, 1991, now abandoned,which is a division of Ser. No. 07/569,764, filed Aug. 22, 1990, nowU.S. Pat. No. 5,004,763, which is a continuation of Ser. No. 07/288,578filed Dec. 22, 1988, now abandoned.

This invention relates to a water base erasable ink composition for usein writing with a marking pen which forms readily erasable writings onan impervious writing surface.

There is already known a variety of ink compositions for use in writingwith a marking pen which forms on an impervious writing surface, such asof enamel, resin or metal, writings erasable by wiping lightly with drycloth or paper. These erasable ink compositions usually contain anadditive called a separating agent together with an organic solvent, apigment and a resin.

For example, there is described in Japanese Patent Publication No.62-9149 an erasable ink composition which contains an aliphatic dibasiccarboxylic acid diester and an aliphatic monobasic carboxylic acid estertogether with a surfactant, a polyester resin and a saturated fatty acidtriglyceride dissolved in an organic solvent.

Like the above exemplified erasable ink composition, most of theconventional erasable ink compositions contain ketones or alcohols as anorganic solvent, among which ketones are very toxic. Methanol is alsotoxic and smells bad. Ethanol is less toxic, but expensive.

On the other hand, a water base erasble ink composition is also knownwhich contains a resin emulsion such as a polyvinyl acetate emulsion asa separating agent together with a dyestuff or a pigment as a coloringagent, and a surfactant. However, when writings are formed with such anink composition on an impervious surface and dried, the resin emulsionforms a continuous adhesive film on the impervious surface, as is thecase with a so-called known strippable paint. Consequently the writingis not so easily separated or erased from the surface by light wiping.Moreover, when the writing is rather strongly wiped, it is separated asa continuous film from the surface. Namely, even when the writing iswiped only at a part thereof, it often happens that the entire writingis separated from the writing surface.

The present inventors have made intensive investigations to solve theabove-mentioned problem involved in the prior erasable ink compositions,either water base or oil base, and found that a water base inkcomposition which contains a specific combination of a separating agentand a water soluble resin provides writings on an impervious surfacewhich can be readily erased only at wiped portions.

Therefore, it is an object of the invention to provide a water baseerasable ink composition for use in writing with a marking pen whichforms writings readily erasable only at wiped portions.

According to the invention, there is provided a water base erasable inkcomposition which comprises:

(a) water as a solvent in amounts of 50-90% by weight;

(b) a coloring agent dispersed or dissolved in water in amounts of 1-30%by weight;

(c) an aqueous emulsion of at least one nonvolatile or only slightlyvolatile compound which is liquid at room temperatures and is selectedfrom the group consisting of aliphatic carboxylic acid esters, higherhydrocarbons and higher alcohols in dry amounts of 1-25% by weight; and

(d) a water soluble resin or a water-solubilized resin which is filmforming at room temperatures in amounts of 0.1-15% by weight.

Water is used as a solvent in the ink composition of the invention, andis contained usually in amounts of 50-90% by weight, preferably inamounts of 60-80% by weight.

As a coloring agent, any pigment may be used, and the pigment usableincludes, for example, carbon black, phthalocyanines such as copperphthalocyanine blue, azo pigments, quinacridones, anthraquinones,dioxazines, indigos, thioindigos, perynones, perylenes, indolenones andazo-azomethines.

A variety of aqueous pigment dispersions is commercially available, andthey may be preferably used in the invention. The dispersion usuallycontains a dispersant or a surfactant, so that the ink composition ofthe invention may contain such a dispersant or a surfactant when thedispersion is used in .the ink composition. The dispersant is usually apolymeric one and is contained in the dispersion usually in amounts of1-300 parts by weight, preferably in amounts of 5-100 parts by weight,per one part by weight of pigments. A dyestuff may also be used as acoloring agent, preferably a water soluble dyestuff.

The content of coloring agents in the ink composition may be selecteddepending upon the agent used or the darkness of writings required.However, when the content of coloring agents is too much, the pigmentdeposits in the ink composition, or the resultant ink composition has anexcessively high viscosity, so that the composition clogs a pen tip, orwrites bad. On the other hand, when the content of coloring agents istoo small, the ink composition fails to form writings of an appropriatedarkness. Therefore, the coloring agent is contained in the inkcomposition usually in amounts of 1-30% by weight, preferably in amountsof 5-20% by weight.

The ink composition of the invention contains a separating agent whichis an aqueous emulsion of at least one nonvolatile or only slightlyvolatile compound which is liquid at room temperatures and is selectedfrom the group consiting of aliphatic carboxylic acid esters, higherhydrocarbons and higher alcohols.

The aliphatic carboxylic acid ester includes monobasic carboxylic acidesters, dibasic carboxylic acid diesters, mono- or diesters of dihydricalcohols, and mono-, di- or triesters of trihydric alcohols. Morespecifically, there may be used monobasic carboxylic acid esters,preferably higher fatty acid esters such as ethyl oleate, butyl laurate,hexyl laurate, isostearyl laurate, oleyl 2-ethylhexanoate, ethylisostearate, butyl stearate, isopropyl myristate, butyl palmitate,isooctyl palmitate, isooctadecyl palmitate, isooctyl stearate andisooctadecyl stearate; dibasic acid diesters such as dodecanedioic aciddioctyl ester, dipropyl adipate, dioctyl sebacate or dioctyl azelate;dihydric alcohol esters such as propylene glycol monostearate orpropyleneglycol didecanoate; and trihydric alcohol esters such asnatural or synthetic fatty acid triglycerides, for example, caproic acidtriglyceride, carprylic acid triglyceride, lauric acid triglyceride,2-hexyldecanoic acid triglyceride or the like. The triglyceride may be amixed triglyceride in which the fatty acid components are different fromeach other. Further, the triglyceride may be used singly or as amixture. Fatty acid trimethylolpropane triesters such as triisostearatemay also be used.

The higher hydrocarbon used as a separating agent is not specificallylimited, but may be exemplified by liquid paraffin and squalane.Oxydized polyethylene wax may also be used. The higher alcohol used isalso not specifically limited, but may be exemplified by hexyl alcohol,octyl alcohol and lauryl alcohol.

Aqueous emulsions of the aliphatic acrboxylic acid esters, higherhydrocarbons or higher alcohols may be prepared by conventionalemulsifying methods, and are commercially available. The emulsion may beused singly or as a mixture of two or more.

The emulsion is contained in the ink composition of the invention sothat the aliphatic carboxylic acid ester, higher hydrocarbon, higheralcohol or a mixture of two or more of these is contained in dry amountsof 1-20% by weight, preferably in amounts of 5-15% by weight, based onthe ink composition. When the amount of the liquid compound, i.e., theester, hydrocarbon or alcohol, is too small, the resultant inkcomposition is not readily erasable or seaparable from an impervioussurface, whereas when the amount of the liquid compound is too large,the resultant ink composition writes bad or it stains a writing surface.

The ink composition of the invention contains a resin which is watersoluble and film forming at room temperatures so that when writings havebeen formed and dried on an impervious writing surface, the writing hasa continuous resin layer which contains the coloring agent therein andwhich is separated from a layer of the separating agent, thereby toprovide the writing with a ready separability or a high erasability. Thewater soluble resin also provides the ink composition with a viscositysuitable for writing and provides writings with a suitable adhesion to awriting surface.

One of the preferred water soluble resins is by nature water solubleresins such as polyvinylpyrrolidone or polyvinylalcohol having apolymerization degree of 100-3000 and a saponification degree of notless than 50 mole %, with the latter preferred of the two. Natural watersoluble resins may be used such as gum arabic.

In the invention, however, a resin which is water-solubilized and filmforming at room temperatures is more preferably used as a water solubleresin in a broader sense. The water-solubilized resin is herein thespecification defined as resins which are by nature water insoluble butare made water-solubilized by salt formation with inorganic or organicbases, such as alkali metal salts, e.g., sodium or potassium salts,ammonium salts or amine salts.

The water-solubilized resin usable may be exemplified by acrylic resins,vinyl acetate copolymers, polyurethane resins, styrene-maleic anhydrideresins, maleic oils, maleic polybutadienes, alkyd resins, maleic alkydresins and maleic rosin ester resins, all in the form of salts asabove-mentioned. Among the above exemplified, water-solubilized vinylacetate copolymers, alkyd resins inclusive of maleic alkyd resins, andpolyurethane resins are most preferred.

The vinyl acetate copolymer usable, in particular, includes copolymersof vinyl acetate with unsaturated carboxylic acids such as acrylic acid,methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconicacid, crotonic acid or citraconic acid. The vinyl acetate copolymer maycontain further comonomers such as vinyl esters other than vinyl acetate(e.g., vinyl propionate), vinyl hydrocarbons (e.g., ethylene, propylene,butene, styrene, α-methylstyrene), acrylic or methacrylic acid esters(e.g., methyl acrylate, ethyl acrylate, butyl acrylate, methylmethacrylate, ethyl methacrylate or dimethyl maleate). The vinyl acetatecopolymer may be a graft one with the monomers as above described ontopolyvinyl acetates.

Preferred vinyl acetate copolymers may be exemplified by vinylacetate-acrylic acid copolymer, vinyl acetate-methacrylic acidcopolymer, vinyl acetate-styrene-acrylic acid copolymer, vinylacetate-styrene-maleic anhydide copolymer, vinyl acetate-acrylicacid-methyl acrylate copolymer, vinyl acetate-methacrylic acid-methylacrylate copolymer, vinyl acetate-acrylic acid-ethyl acrylate copolymer,vinyl acetate-methacrylic acid-methyl methacrylate copolymer and vinylacetate-maleic anhydide copolymer. The vinyl acetate coplymers areusually water insoluble, however, the inorganic or organic salts thereofare water soluble. Theses water-solublized copolymers are commerciallyavailable.

Similarly, the water-solublized alkyd resins may be prepared bycondensation of excessive unsaturated carboxylic acids with polyhydricalcohols, and salt formation with alkali metals, ammonium bases ororganic amines. The water-solubilized urethane resins may be prepared bysalt-formation of pendant carboxylic groups in the polymer chain withalkali metals, ammonium bases or organic amines. These water-solubilzedalkyd resins and urethane resins are also commercially available.

The water soluble or water-solubilized resin is contained in the inkcomposition in amounts of 0.1-15% by weight, preferably in amounts of0.3-10% by weight, based on the ink composition. When the amount of theresin is too large, the resultant ink composition has an excessivelyhigh viscosity so that it writes bad but also writings formed therewithis not readily erased.

A further water base erasable ink composition is provided in accordancewith the invention.

The ink composition comprises:

(a) water as a solvent in amounts of 50-90% by weight, preferably of60-80% by weight;

(b) a coloring agent dispersed or dissolved in water in amounts of 1-30% by weight, preferably of 5-20% by weight;

(c) an aqueous emulsion of at least one nonvolatile or only slightlyvolatile compound which is liquid at room temperatures and is selectedfrom the group consisting of aliphatic carboxylic acid esters, higherhydrocarbons and higher alcohols in dry amounts of 1-20% by weight,preferably of 5-15% by weight, as a separating agent; and

(d) an aqueous emulsion or a hydrosol of a water insoluble resin whichis film forming at room temperatures in solid amounts of 0.1-15% byweight.

The coloring agent and the separating agent have been describedhereinbefore.

In this water base erasable ink composition of the invention, filmforming aqueous emulsions or hydrosols of resins which are by naturewater insoluble is used in place of the aforesaid water soluble resinsor water-solubilized resins.

As the above by nature water insoluble resins, there may be mentioned,for example, polyvinyl acetates, vinyl acetate copolymers, alkyd resinsand urethane resins, with polyvinyl acetates and vinyl acetatecopolymers most preferred. Preferred examples of the latter are the sameas described hereinbefore.

The emulsion or hydrosol is contained in the ink composition in dryamounts of 0.1-15% by weight, preferably in amounts of 0.3-10% byweight, based on the ink composition, based on the same reason as beforedescribed regarding water soluble or water-solubilized resins.

The emulsion or hydrosol of water insoluble resins forms a continuousresin layer which contains the coloring agent therein and which isseparated from a layer of the separating agent, so that writings formedon an impervious surface is readily erasable. Further, since the resinis water insoluble, the ink composition provides highly water resistantwritings, or writings readily and stably erasable under high humidity.

When desired, a mixture of water soluble or water-solubilized resinswith the emulsion or hydrosol of water insoluble resins may be used intotal solid amounts of 0.1-15% by weight based on the ink composition.

The ink composition of the invention may contain a water solublepolyhydric alcohol to assist the separation of writings from writingsurface. The polyhydric alcohol usable includes, for example, ethyleneglycol, diethylene glycol, triethylene glycol, propylene glycol,dipropylene glycol, tripropylene glycol, polyethylene glycol having amolecular weight of about 200-600, polypropylene glycol having amolecular weight of about 1000-3000, glycerine and trimethylolpropane.The polyhydric alcohol may be contained in amounts of not more than 20%by weight, preferably in amounts of not more than 10% by weight, basedon the ink composition. When the amount of the polyhydric alcohol is toolarge, the resultant ink composition has an excessively large viscosityand writes bad.

A variety of surfactants, either anionic, nonionic, cationic orampholytic, may also be incorporated in the ink composition as a writingseparation assintance. However, polyoxyethylene carboxylic acid,sulfonic acid, sulfate or phosphate nonionic or anionic surfactants,ampholytic betaine surfactants or fluorinated surfactants are preferred.The amount of surfactants may be not more than 10 % by weight,preferably in the range of 0.2-5% by weight based on the inkcomposition. The use of exessive amount deteriolates the erasability ofthe ink composition.

The surfactant assists the separation of the oily layer from the resinlayer when writings are formed. Moreover, the surfactant provides alevelling effect with writings formed but also prevents the emulsionfrom being unevenly distributed on a writing surface when writings areformed, so that the dried writing is evenly erasable. From thesestandpoints, fluorinated surfactants are most preferred.

Although the invention is not limited by any theory, however, whenwritings are formed on an impervious writing surface with a marking pen,and when the water has been evaporated or the writing has been dried,the resin forms a film colored with the pigment, while the emulsion ofthe separating agent is broken to form a continuous oily layer betweenthe impervious writing surface and the resin film, and therefore thewriting is separable or erasable from the surface by being wiped.

Lower aliphatic alcohols may be contained in the ink composition so thatwritings are readily dried when formed. However, the alcohol must notbreak the emulsion in the ink composition, and therefore the amount maybe not more than 15% by weight, preferably in the range of 1-10% byweight, based on the ink composition. The preferred alcohol may beethanol, propanol or butanol.

The ink composition may further contain any conventional additives usedin water base ink compositions, such as pH controllers or anticorrosionagents.

As above set forth, the erasable ink composition of the invention isvery little toxic, and is attended by very little bad and irritant smellsince it is water base. Further, the ink composition of the inventioncontains a specific combination of a separating agent and a watersoluble or water-solubilized resin, or an emulsion or a hydrosol ofwater-insoluble resin therein. Therefore, when writings are formedtherewith on an impervious writing surface and dried, the separatingagent forms a continuous oily layer on the surface, and separates thelayer of resins which contains a coloring agent therein from the writingsurface, and as results, the writing is readily separated from thewriting surface.

In particular, the separating layer is not a solid film, but an oilyone, so that when the writing is wiped only partly, the wiped portionsonly are erased. Further, since the separating layer is composed ofnonvolatile or only slightly volatile liquid compound, writings arereadily erasable after long standing.

When the ink composition contains a by nature water insoluble resin in awater-solubilized form, or more preferably as a hydrosol or an emulsion,the resin forms a colored layer which is highly water resistant as wellas readily and stably erasable irrespectively of ambientnt humidityconditions.

The invention will now be described with reference to examples, however,which are not to be construed as limiting to the invention.

At first, some examples of preparations of aqueous emulsions ofseparating agents are described.

Reference Example 1

An amount of 67 parts by weight of water, 30 parts by weight of butylstearate and 8 parts by weight of a nonionic surfactant (Neugen EA-120by Daiichi Kogyo Seiyaku K. K., Japan, HLB of 12) were mixed togetherand emulsified with a homogenizer, to prepare an aqueous emulsion ofbutyl stearate.

Reference Example 2

An amount of 71 parts by weight of water, 25 parts by weight ofdodecanedioic acid dioctyl ester, 0.8 parts by weight of a nonionicsurfactant (Span 80 by Kao K. K., Japan) and 0.8 parts by weight of anonionic surfactant (Tween 80 by Kao K. K., Japan) were mixed togetherand emulsified with a colloid mill, to prepare an aqueous emulsion ofdodecanedioic acid dioctyl ester.

Reference Example 3

An amount of 65 parts by weight of water, 30 parts by weight of liquidparaffin and 5 parts by weight of a nonionic surfactant (Nonion H8-206by Nippon Yushi K. K., Japan) were mixed together and emulsified with acolloid mill, to prepare an aqueous emulsion of the liquid paraffin.

Preparation of Ink Compositions I

Water base ink compositions were prepared as shown below. Parts (byweight) of pigment dispersions are the amount of the dispersion used toprepare 100 parts of ink compositions, and percents are those ofeffective (dry or solid) amounts of ingredients used in the inkcomposition.

    ______________________________________                                        Ink Composition 1                                                             Coloring Agent (carbon black dispersion.sup.1))                                                      50 parts                                               Carbon black           7.5%                                                   Resin                  1.0%                                                   Water soluble acrylic resin                                                   Separating Agent                                                              Butyl stearate         7.0%                                                   Isopropyl myristate    3.0%                                                   Surfactant                                                                    Nonionic               0.5%                                                   Fluorinated            0.3%                                                   Drying Assistance      8.0%                                                   Isopropanol                                                                   Comparative Ink Composition 2                                                 Coloring Agent (carbon black dispersion.sup.2))                                                      50 parts                                               Carbon black           5.5%                                                   Resin                  --                                                     None                                                                          Separating Agent                                                              Butyl palmitate        5.0%                                                   Dioctyl dodecanedioate 5.0%                                                   Liquid paraffin        3.0%                                                   Surfactant                                                                    Nonionic               0.7%                                                   Fluorinated            0.2%                                                   Drying Assistance      5.0%                                                   Ethanol                                                                       Ink Composition 3                                                             Coloring Agent (Special Black TU Paste.sup.3))                                                       20 parts                                               Carbon black           5.0%                                                   Resin                  2.5%                                                   Polyvinyl alcohol                                                             Separating Agent                                                              Butyl isostearate      8.0%                                                   Fatty acid triglyceride                                                                              3.0%                                                   Surfactant             0.3%                                                   Fluorinated                                                                   Ink Composition 4                                                             Coloring Agent (Copper Phthalocyanine                                                                20 parts                                               Blue.sup.4))                                                                  Copper phthalocyanine blue                                                                           6.0%                                                   Resin                  0.5%                                                   Gum arabic                                                                    Separating Agent                                                              Butyl stearate         5.0%                                                   Butyl palmitate        3.0%                                                   Dioctyl sebacate       3.0%                                                   Surfactant                                                                    Aionic                 0.5%                                                   Ampholytic betaine     0.5%                                                   Fluorinated            0.3%                                                   Drying Assistance      5.0%                                                   Isopropanol                                                                   Ink Composition 5                                                             Coloring Agent (Flexonyl Blue AN.sup.5))                                                             20 parts                                               Pigment                5.0%                                                   Resin                  2.0%                                                   Polyvinyl alcohol                                                             Separating Agent       8.0%                                                   Isopropyl myristate                                                           Separating Assistance  2.0%                                                   Polyethylene glycol (average                                                  molecular weight of 300)                                                      Surfactant             0.4%                                                   Fluorinated                                                                   Drying Assistance      5.0%                                                   Ethanol                                                                       Ink Composition 6                                                             Coloring Agent (Flexonyl Red FGR-LA.sup.5))                                                          20 parts                                               Pigment                5.0%                                                   Resin                  5.0%                                                   Water soluble acrylic resin                                                   Separating Agent                                                              Dioctyl azelate        5.0%                                                   Diisopropyl adipate    5.0%                                                   Surfactant                                                                    Nonionic               0.4%                                                   Anionic                0.2%                                                   Drying Assistance      6.0%                                                   Isopropanol                                                                   Ink Composition 7                                                             Coloring Agent         5.0%                                                   Blue No. 1                                                                    Resin                  3.5%                                                   Polyvinyl alcohol                                                             Separating Agent       10.0%                                                  Butyl stearate                                                                Surfactant             0.4%                                                   Fluorinated                                                                   Drying Assistance      6.0%                                                   Isopropanol                                                                   Ink Composition 8                                                             Coloring Agent (carbon black dispersion.sup.1))                                                      25 parts                                               Carbon black           5.0%                                                   Resin                  10.0%                                                  Polyvinyl alcohol                                                             Separating Agent       10.0%                                                  Butyl stearate                                                                Surfactant             2.0%                                                   Nonionic                                                                      Comparative Ink Composition 9                                                 Coloring Agent (carbon black dispersion.sup.1))                                                      25 parts                                               Carbon black           5.0%                                                   Resin                  10.0%                                                  Water soluble acrylic resin                                                   Separating Agent       10.0%                                                  Butyl stearate                                                                Surfactant             2.0%                                                   Nonionic                                                                      Comparative Ink Composition 10                                                Coloring Agent (carbon black dispersion.sup.2))                                                      25 parts                                               Carbon black           5.0%                                                   Resin                  --                                                     None                                                                          Separating Agent       10.0%                                                  Butyl stearate                                                                Surfactant             2.0%                                                   Nonionic                                                                      ______________________________________                                         Notes:                                                                        .sup.1) Aqueous dispersion composed of 15% by weight of carbon black, 65%     by weight of water and 20% by weight of amine salts of styrenebutyl           acrylatemethacrylic acid copolymer.                                           .sup.2) Aqueous dispersion composed of 10% by weight of carbon black, 67%     by weight of water, 20% by weight of water soluble acrylic resins, 2% by      weight of ammonia water and 1% by weight of surfactants.                      .sup.3) Aqueous dispersion of carbon black.                                   .sup.4) Aqueous dispersion composed of 15% by weight of copper                phthalocyanine, 75% by weight of water and 10% by weight of ammonium salt     of styrenemethyl methacrylatehydroxymethyl methacrylateacrylic acid           .sup.5) Aqueous dispersion of pigments                                   

Writings were formed on impervious writing surfaces of enamel, and thewriting was left standing at a temperature of 25° C. under a relativehumidity of 60% for five minutes and for 15 days, respectively, and thenwiped lightly with dry cloth, to evaluate erasability of the writingafter five minutes (initial erasability) and after 15 days (standingerasability). The erasability was evaluated with the eyes: A, readilyerasable; B, fairly erasable; C, only slightly erasable; and D, scarcelyerasable. The results are shown in Table 1.

For comparison, the same erasability tests were carried out usingconventional commercially available oil base erasable ink compositions.The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                         Erasability                                                                   Initial                                                                            Standing                                                ______________________________________                                        Conventional  1.sup.1))                                                                              A      A                                                             2.sup.2))                                                                              A      A                                                             3.sup.3))                                                                              A      C                                               Ink Composition                                                                             1        A      A                                                             2*.sup.))                                                                              B      B                                                             3        A      A                                                             4        B      C                                                             5        A      B                                                             6        A      A                                                             7        B      B                                                             8        A      A                                                             9*.sup.) B      C                                                            10*.sup.) C      D                                               ______________________________________                                         Notes:                                                                        .sup.1) Contains ketones as a solvent, commercial products                    .sup.2) Contains alcohols as a solvent, commercial products                   *.sup.) Comparative examples                                             

The water base ink composition of the invention is comparable with theconventional oil base ones in the erasability of writings. Further, theink composition of the invention is superior in erasability both initialand standing to the comparative examples containing no resins therein.

Preparation of Ink Compositions II

Water base ink compositions were prepared as shown below. Percents arethose of effective (dry or solid) amounts of ingredients used in the inkcomposition. The ink composition contained an effective amount ofanticorrosion agents and the balance was water. A dispersant was used toprepare a pigment dispersion and the amount thereof was also shownbelow.

    ______________________________________                                        Ink Composition 1                                                             Coloring Agent       5.0%                                                     Carbon black                                                                  Dispersant           2.0%                                                     Ammonium salts of styrene-butyl                                               acrylate-methacrylic acid                                                     Resin                6.0%                                                     Hydrosol of vinyl acetate-ethyl                                               acrylate-acrylic acid copolymer                                               Separating Agent     10.0%                                                    Butyl stearate                                                                Surfactant           1.0%                                                     Anionic                                                                       Ink Composition 2                                                             Coloring Agent       5.0%                                                     Carbon black                                                                  Dispersant           3.0%                                                     Water solubilized acrylic resin                                               Resin                6.0%                                                     Emulsion of vinyl acetate-                                                    methacrylic acid copolymer                                                    Separating Agent                                                              Butyl stearate       5.0%                                                     Dioctyl dodecanedioate                                                                             5.0%                                                     Surfactant           0.5%                                                     Anionic                                                                       Ink Composition 3                                                             Coloring Agent       6.0%                                                     Phthalocyanine blue                                                           Dispersant           4.0%                                                     Ammonium salts of styrene-maleic                                              acid                                                                          Resin                6.0%                                                     Emulsion of vinyl acetate-maleic                                              acid copolymer                                                                Separating Agent     8.5%                                                     Squalane                                                                      Separating Assistance                                                                              3.0%                                                     Polyethylene glycol (average                                                  molecular weight of 300)                                                      Surfactant           1.5%                                                     Ampholytic                                                                    Ink Composition 4                                                             Coloring Agent       5.5%                                                     Monoazo Red                                                                   Dispersant           2.5%                                                     Nonionic surfactant                                                           Resin                7.0%                                                     Emulsion of polyvinyl acetate                                                 Separating Agent                                                              Lauryl alcohol       5.0%                                                     Fatty acid triglyceride                                                                            6.0%                                                     Surfactant           1.0%                                                     Nonionic                                                                      Ink Composition 5                                                             Coloring Agent       4.0%                                                     Carbon black as a dispersion                                                  Resin                5.0%                                                     Water-solubilized acrylic resin                                               Separating Agent                                                              Octyl stearate       5.0%                                                     Liquid paraffin      6.0%                                                     Separating Assistance                                                                              2.0%                                                     Polyethylene glycol (average                                                  molecular weight of 300)                                                      Surfactant           1.0%                                                     Anionic                                                                       Ink Composition 6                                                             Coloring Agent       5.0%                                                     Carbon black as a dispersion                                                  Resin                6.5%                                                     Emulsion of polyurethane resins                                               Separating Agent     12.0%                                                    Butyl isostearate                                                             Surfactant           0.5%                                                     Anionic                                                                       ______________________________________                                    

In the same manner as before described, initial and standing erasabilityof writings formed on an enamel surface were evaluated. The results areshown in Table 2.

                  TABLE 2                                                         ______________________________________                                                         Erasability                                                                   Initial                                                                            Standing                                                ______________________________________                                        Ink Composition                                                                            1         A      B                                                            2         A      A                                                            3         A      B                                                            4         A      A                                                            5         B      A                                                            6         B      B                                               ______________________________________                                    

The water base ink composition of the invention is comparable with theconventional oil base ones in the erasability of writings.

Preparation of Ink Compositions III

The following water base ink compositions 7 to 10 were prepared. Thecompositions 8 to 10 were comparative examples.

    ______________________________________                                        Ink Composition 7                                                             Coloring Agent                                                                Carbon black          4.0%                                                    Dispersant                                                                    Water-solubilized acrylic acid-                                                                     2.0%                                                    styrene copolymer                                                             Resin                                                                         Hydrosol of vinyl acetate-methyl                                                                    7.0%                                                    methacrylate-acrylic acid copolymer                                           Separating Agent                                                              Butyl palmitate       10.0%                                                   Surfactant                                                                    Anionic               1.0%                                                    Comparative Ink Composition 8                                                 Coloring Agent                                                                Carbon black          4.0%                                                    Dispersant                                                                    Water-solubilized acrylic acid-                                                                     2.0%                                                    styrene copolymer                                                             Resin                                                                         Water soluble polyvinyl alcohol                                                                     7.0%                                                    Separating Agent                                                              Butyl palmitate       10.0%                                                   Surfactant                                                                    Anionic               1.0%                                                    Comparative Ink Composition 9                                                 Coloring Agent                                                                Carbon black          4.0%                                                    Dispersant                                                                    Water-solubilized acrylic acid-                                                                     2.0%                                                    styrene copolymer                                                             Resin                                                                         Water soluble polyvinylpyrrolidone                                                                  7.0%                                                    Separating Agent                                                              Butyl palmitate       10.0%                                                   Surfactant                                                                    Anionic               1.0%                                                    Comparative Ink Composition 10                                                Coloring Agent                                                                Carbon black          4.0%                                                    Dispersant                                                                    Water-solubilized acrylic acid-                                                                     2.0%                                                    styrene copolymer                                                             Resin                                                                         Water-solubilized styrene-maleic                                                                    7.0%                                                    acid copolymer                                                                Separating Agent                                                              Butyl palmitate       10.0%                                                   Surfactant                                                                    Anionic               1.0%                                                    ______________________________________                                    

Writings were formed on impervious writing surfaces of enamel, and thewriting was left standing at a temperature of 25° C. under variedrelative humidities to evaluate erasability and "elongation" of thewriting when it was wiped on the writing surface. The elongation is ameasure of water resistance of writing since writing is more elongatedor extended on the writing surface under a high humidity when it iswiped as it is less water resistant. The elongation of writing wasevaluated by four grades: A, not elongated; B: slightly elongated, buterased; C: elongated and only slightly erased; and D, remarkablyelongated and scarcely erased. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                    Erasability                                                                          Elongation of Writings                                                 Relative Humidity (%)                                                         60     55       67      80                                        ______________________________________                                        Ink Composition                                                                         7       A        A      A     A                                     Comparative                                                                             8       A        A      C     D                                               9       B        B      D     D                                               10      B        A      A     A                                     ______________________________________                                    

The water base ink composition containing a hydrosol of a vinyl acetatecopolymer forms writings readily erasable without elongationirrespectively of humidity, but the ink compositions containing watersoluble resins form writings elongated by wiping under high humidity.When an ink composition contains a water-solubilized resin, writingsformed therewith are not elongated by wiping, however, it is a littleless erasable than the composition containing a hydrosol of a vinylacetate copolymer.

What is claimed is:
 1. A water base erasable ink composition for use inmarking pens and for writing on an impervious writing surface, whichconsists essentially of:(a) water as a solvent; (b) a pigment dispersedin water in an amount of 1-30% by weight; (c) an aqueous emulsion of afatty acid ester which is nonvolatile or only slightly volatile andliquid at room temperatures, which functions as a separating agent, andwhich is selected from the group consisting of ethyl oleate, butyllaurate, hexyl laurate, isostearyl laurate, oleyl 2-ethylhexanoate,ethyl isostearate, butyl stearate, isopropyl myristate, butyl palmitate,isooctyl palmitate, isooctadecyl palmitate, isooctyl stearate andisooctadecyl stearate, in a dry amount of 5-15% by weight; and (d) awater-solubilized resin which is at least one of an acrylic resin, avinyl acetate copolymer other than vinyl acetate-acrylic acid copolymer,a polyurethane resin, a styrene-maleic anhydride resin, a maleic oil, amaleic polybutadiene, an alkyd resin, a maleic alkyd resin and a maleicrosin ester resin, each in the form of a salt with an inorganic or anorganic base, and which is film forming at room temperatures, in anamount of 0.1-15% by weight.
 2. The ink composition as claimed in claim1 wherein the water solubilized vinyl acetate copolymer is a vinylacetate copolymer with an unsaturated carboxylic acid, and optionallywith a further comonomer which is at least one of a vinyl ester otherthan vinyl acetate, a vinyl hydrocarbon, an acrylic acid ester, amethacrylic acid ester and dimethyl maleate.
 3. The ink composition asclaimed in claim 2 wherein the unsaturated carboxylic acid is at leastone of acrylic acid, methacrylic acid, maleic acid, maleic anhydride,fumaric acid, itaconic acid, crotonic acid and citraconic acid.
 4. Theink composition as claimed in claim 2 wherein the vinyl ester is vinylpropionate.
 5. The ink composition as claimed in claim 2 wherein thevinyl hydrocarbon is at least one of ethylene, propylene, butene,styrene and α-methylstyrene.
 6. The ink composition as claimed in claim2 wherein the acrylic acid ester is at least one of methyl, ethyl andbutyl esters.
 7. The ink composition as claimed in claim 2 wherein themethacrylic acid ester is at least one of methyl, ethyl and butylesters.
 8. The ink composition as claimed in claim 1 wherein the watersolubilized vinyl acetate copolymer is at least one of vinylacetate-methacrylic acid copolymer, vinyl acetate-styrene-acrylic acidcopolymer, vinyl acetate-styrene-maleic anhydride copolymer, vinylacetate-acrylic acid-methyl acrylate copolymer, vinylacetate-methacrylic acid-methyl acrylate copolymer, vinylacetate-acrylic acid-ethyl acrylate copolymer, vinyl acetate-methacrylicacid-methyl methacrylate copolymer and vinyl acetate-maleic anhydridecopolymer.
 9. The ink composition as claimed in claim 1 wherein apolyhydric alcohol is present in an amount of not more than 20% byweight based on the ink composition.
 10. The ink composition as claimedin claim 1 wherein a lower aliphatic alcohol is present in an amount ofnot more than 15% by weight based on the ink composition.
 11. The inkcomposition as claimed in claim 1 wherein the water-solubilized resin isin an amount of 0.3-10% by weight.
 12. The ink composition as claimed inclaim 1 which further comprises an anionic, a nonionic, a cationic, oran ampholytic surfactant in an amount of not more than 10% by weightbased on the ink composition.
 13. A water base erasable ink compositionfor use in marking pens and for writing on an impervious writingsurface, which consists essentially of:(a) water as a solvent; (b) apigment dispersed in water in an amount of 1-30% by weight; (c) anaqueous emulsion of a fatty acid ester which is nonvolatile or onlyslightly volatile and liquid at room temperatures, which functions as aseparating agent, and which is selected from the group consisting ofethyl oleate, butyl laurate, hexyl laurate, isostearyl laurate, oleyl2-ethylhexanoate, ethyl isostearate, butyl stearate, isopropylmyristate, butyl palmitate, isooctyl palmitate, isooctadecyl palmitate,isooctyl stearate and isooctadecyl stearate, in a dry amount of 1-15% byweight; and (d) a water soluble resin which is at least one of polyvinylalcohol, polyvinylpyrrolidone and gum arabic and which is film formingat room temperatures, in an amount of 0.1-15% by weight.
 14. The inkcomposition as claimed in claim 13 wherein a polyhydric alcohol ispresent in an amount of not more than 20% by weight based on the inkcomposition.
 15. The ink composition as claimed in claim 13 wherein alower aliphatic alcohol is contained in an amount of not more than 15%by weight based on the ink composition.
 16. The ink composition asclaimed in claim 13 wherein the water-solubilized resin is in an amountof 0.3-10% by weight.
 17. The ink composition as claimed in claim 13which further comprises an anionic, a nonionic, a cationic, or anampholytic surfactant in an amount of not more than 10% by weight basedon the ink composition.